Water-insoluble azo dyestuffs and fiber dyed therewith



Patented Nov. 14, 1939 UNITED STATES WATERJNSOIQUBLE Azo D ESTUFFsANn FIBER DYED' THEREWITH Leopold Laska,: OflEenbach-on-theeMain;iArthur Zitscher, Kronberg in=Taunus, ,and Ru d ol-; Heil Ofienbach-on-the-Main, Germanya assignors; I to, Gneneral Aniline, Works, Inc.', New York-, .N. Y., acorporatio'n of Delaware No D'rawing. Application August .11, 1 937.,l Sei'ial-f No- 158,618.v In Germany August-12;;1936.; a i

12 claims. (oi. 260-2o4) The .presentinvention relates to -water-insolu'- ble .azo dyestufis. and to fiber dyed therewith; more: particularly, it relates :to 1 dyestuffs of I the following; general formula:

wherein n stands for one on the numbersi and=.2, the Xs stand for substituents, R means a naph-.v

- thalene, carbazolavbenzocarbazole or anthracene nucleus and R1 a radical of the benzene, naphthalene or diphenylseries.

We have found that valuable azodyestufis insoluble in'water maybe-obtained by coupling-in substance, on a fiber or on a substratum adapted I for the productionof-lakes; the diazo compound of a 1-amin0-4-nit'rilobe'nzene. substituted "in. 2- and 5-position with an ortho-hydroxyaryl carboxylic acid arylamide, the dyestuff fcompo-n. nents not containing any solubilizing; groupssuch as sulfonic acid or'carboxylic acid groups.

When made in substance the newfdyestufis may be used for the preparation of valuable pigements; they are, however, also particularlys'uit; able for the production of insoluble dyestufis on the fiber, both native and/regenerated 'cellulosef fibers and animal fibers, by the ice color method or by one oi the usual printing methods, for instance in direct printing or according to the t known printing process with use ofnitrosamines or diazoaminoecompounds or the like. 7

Over comparable combinations described in. 1

The following examples serve toillustratethethereto: v i I (1) Well boiled, dried cotton yarn is impreg. nated with a solution containing per liter 4 grams of. lene, 10 cc. of caustic soda solution .of 34 BQ and 10 cc; of Turkey red oil of .150Aper centg strength, well squeezed and developed with a'de-- veloping solution which has been rendered feeblygj acid with acetic acid and containing per liter the diazo compound from 1.82grams of la-amino 1- (2.3'-hydroxynaphthoylamino) enaphtha Y A blue-red dyeing of very goodiastness tq light 5511s obtained.

By using 2.3 hydroxynaphthoyleaminobenzenez as grounding component a1yellow-red: dyeing likewise of very good fastness to light is obtained.

(2) Desized..v and bleached cotton piece; goods are padded on a foulard with a solution contaim.

ingeper liter 15 grams of".2.3ehydroxynaphthoylaminobenzene, 22.5 cc. of caustic soda solution of; 34?. .B. and 22.50; ofJIfurkeyredoil- Thelmpregnate'd'il and dried material is then. passed. throughfa-develo'ping.solution'iwhich contains per liter the diazo-compound frorn' 12. grams of 1- amino-2.5;dichloroAenitrilobenzeneand is feebly, I

acid with acetic. acid..' After a. short passage.

through. the-air "the, material, is. rinsed several times 'vv'ith 'cold water and finally. soaped, rinsed and dried as usual.

A yellowred dyeing. of. verygood fastness to. light is obtained.

(3). Desized. andibleache dlcottoni piece. goods..

are impregnated on a foulard with a padding solution-prepared in- 'theusual manner 'frompl2 grams of 2.3 hydroxynaphthoyl-aminobenzene per literand. dried. The material is then printed with a red resist of the following composition:

8 grams of 1-amino-3-methyl-fi-chlorol-nitrilobenzene in'the fornr of a"stabilized diazonium 1 compound,---3l0--grams of water, grams iof cl az n um chloride from 9, rams of minoe4'pmethoxy-diphenylamine and containing magnesium sulfate; After a short passage" through the airthe material is passed through a bath having terial is thoroughly rinsed hot and cold,',soap ed for a short time at boiling'temperature, rinsed,

soaped again, rinsed and dried. invention, but they are not intended to limitit 111b?ny g efiectYQn b ground" is a =-"-"o aine.,.I

amino) .-2-methyle4-chlorobenzene are, dissolved with 4.5 cc. of'caustic soda solution of 34 B. and

cellulose 'wasteliquor in the form of a powder,

so as to produce 1, liter of padding solution.

lj Degummed spun silk is'impregnated in this solution in alproportion ofgoods. to liquor of 1:30, squeezed and then developed in a solutionwhich has been rendered neutral to. Congo paper by addition of sodiumacetate and contains the acid 45. 3 cc. offflurkey redoiliof-fio per-cent. strength. with addition of one of the usual protective agents fo r silk, for instance 1.5. grams of purified sulfite 35 atemperature of 50.%C.,and.containing'l5wcctoi;

' a bisulfi'te solutionof-38 B perliter. The ma- U. S. Patent No. 1,759,259 the new dyestufis have the advantage of an improved fastness" taught.

diazonium sulfate from 2.2 grams of 1-amino-3- methoxy-6-trifluoromethyl-4-nitrilobenzene per liter, a small quantity of acetic acid being added for the coupling. The material is rinsed, acidilied and soaped at boiling temperature. A yellow-red dyeing of very good fastness to light is obtained.

() Desized and bleached cotton piece goods are printed with the following paste:

Grams The potassium compound of 3-methyl-6- chloro 4 nitrilobenzene 1 nitrosamine (aqueous paste with a content of 44.9 per cent. of pure base and containing 4.2

- for 3 minutes in the moist state or exposed to air over-night and subsequently passed through a' bath having a temperature of 80 C.-90 C.

and containing 20 grams of acetic acid of 50 per cent. strength per liter, rinsed and soaped.

A yellowish-red print of very good fastness to light is obtained;

"with a solution of 45.5 parts by weight of 1-(2.3- .hydroxynapthoylamino) 2 methoxy 5 bromobenzene in dilute caustic soda solution to which there have been added the amount of sodium acetate sufficient for binding the excess of mineral acid, and Turkey red oil. The precipitated dyestufl is filtered with suction and washed well When worked up with a substratum in the usual manner, advantageously in v the form of a paste, it yields a red lake of a high degree of fastness to light.

(7 .Pre-bleached linen piece goods are impregnated on a foulard with a solution containing per liter 20 gramsof 1-(2'-hydroxycarbazole- 3' carbonylamino) 4 chlorobenzene 20 cc. of caustic soda'solution of 34 B. and 30 cc. of Turkey red oil, well squeezed and dried. The dyeing is then developed on a foulard in a solution containing the diaz onium chloride from 3.4 grams of 1 amino 2.5 dimethoxy 4 nitrilobenzene and aluminium sulfate. After developing, the material is rinsed, soaped, rinsed again and dried.

A reddish-brown dyeing of very good fastness to light is obtained.

. The following table illustrates a number of combinations which may beprepared by this invention and the shades contained:

Dlazo-compound from- Coupled W1th Shade 2-hydro ynaphthalene-3-carbony1- 1-.amino-5-methy1-2-chloro-4-nitrilobeuzene l-fimmnmnhmfilpnfi ll s -red.

I) 2-m'ninnnanhfhalpnn Red, I) l-amino-i-methoxy-benzene Do. Dn l-amino-4-ethoxybenzene. Blue-red. Dn l-amiuo-2-methoxy-benzene-- Bluish-red.

- Dn l-amino-2-ethoxybeuzeue- Yellowish-red.

- Dn l-amino-Z-methyl-benzene Do.

Dn 1-amiuo-4-methoxy-2-methylbeuzene Full red n 1-amino-2.4-dimethoxy-fi-chlorobenzene. Red.

. D0 l-amino-2.5-dimethoxy-benzene Yellowish-red.

' Dn l-amino-S-chlorobenzene 0.

Dn 1-amino-4-methoxy-naphthalene. Brownish Bordeaux.

' Dn l-amiuo-2.4-dimethoxybenzene Copper red.

' D l-amino-2..B-dimethoxy-4-chlorobenzene. Orange brown.

-Dn l-amino-2.4-dimethoxyr3-chlorobeuzene Yellow-red.

Dn 1-amino-4-methoxy-3-methylbenzene Full red.

2-hydroxy-fi'-bromo-uaphthaleue-3-(carbonyl- Dn Lamina-2.4-dimethoxybenzene) Browuish Bordeaux.

2'-hydroxycarbazole-3-carbony1- Dn l-amino-4-chlorobeuzeue Brown.

- 3 2'-hydroxy-6-methoxynaphthalene-3-(carbonyl- 1 l-amino-z-methoxybeuzene) Currant.

1-amino-5-methy1-2-bromo-4-nitrilobenzene i 2-amjnrmaflhfhalene Red.

Dn l-am1no-4-methoxybenzeue Do. Dn l-amino-4-chlorobenzeue- Yellowish-red.

Dn l-amluo-2.5-dimethoxybe Red. Dn 1-amiuo-4ethoxybenzene-. Bordeaux. 1)" 1-amino-2-methoxy-5-bromob Yellowish-red.

- 2-hydroxycarbazo1e-3-carbonyl- Dn l-amiuo-4-chlorobeuzeue Reddish-browu.

2-hydroxynaphthalene-3-carbonyl- 1-amino-5-methoxy-2-ehloro-4-nitrilobenzene 1-amino-4-methoxybenzene Full red.

, Dn l-amino-4-ethoxybenzene Blue-red.

D l-amind-Z-methylbeuzene Bluish-red. 'Dn l-amiuo-Z-methyl-4-cholorobenzene Yellowish-red.

Dn l-amino-2.5-dimethoxy-benzene Blue-red. D0 2-nminrmnnhfhalpnn Red, l-amino-2-methoxy-5-chloro-4-nitrilobenzeme Amiuobenzene Do. Dn l-am1uo-2-methylbeuzene. Wine-red.

Dn l-amino-2-methoxybenzeue Blue-red.

' Dn l-amino-2ethoxybenzeue Yellowish-red.

Dn l-amino-4-methoxybenzene; Red.

' Dn 'l-amlnoi-ethoxybenzene. Brownish-red. Dn l-amino-4-chlorobenzeue Red. .Dn 1-amluo-2.5-dimethoxy-benzene Wine-red.

Dn l-amiuo-2-methyl-4-chlorobenzene.- Red.

Dn l-amino-2-methoxy-5-bromobeuzene Do. i

. D l-aminnnanhtha'lnnn Bordeaux.

D Q-siminnnaphthalnnn Blulsh-red,

-- -Dn 1-amiuo-4-chlorobenzeue Yellowish-brown.

wherein n stands for one of the numbers 1 and 2, the X5 stand for members of the group consisting of halogen, alkyl, alkoxy, phenoxy, trifiuoromethyl, alkylsulfonyl and dialkylaminosulfonyl, 3 means a member of the group consisting of naphthalene, halogen substituted naphtha lene, alkoxy substituted naphthalene, carbazole, benzocarbazole and anthracene, and R1 a member of the group consisting of radicals of the benzene, naphthalene and diphenyl series, yielding, when produced on the fiber, orange to blue and brown dyeings of good fastness properties, particularly of very good fastness to light.

2. The water-insoluble azo dyestufis of the following general formula:

wherein the X's stand for members of the group consisting of halogen, alkyl, alkoxy,'phenoxy, trifluoromethyl, alkylsulfonyl and dialkylaminosulfonyl and R1 means a radical of the benzene series, yielding, when produced on the fiber, orange to blue and brown dyeings of good fastness properties, particularly of very good fastness to light.

4. The Water-insoluble azo dyestuffs of the following formula:

yielding, when produced on the fiber, yellowishred dyeings of good fastness properties, particularly of very good fastness to light.

5. The water-insoluble azo dyestufi of the following formula:

OCHa

yielding, when produced on the fiber, wine-red dyeings of good fastness properties, particularly of very good fastness to light.

6. The water-insoluble azo dyestufi of the following formula:

OH c1 yielding, when produced on the fiber, bluish-red dyeings of good fastness properties, particularly of very good fastness to light.

7. Fiber dyed with the dyestuffs as claimed in claim 1.

8. Fiber dyed with the dyestuffs as claimed in claim 2.

9. Fiber dyed with the dyestufis as claimed in claim 3.

10. Fiber dyed with the dyestufi as claimed in claim 4.

11. Fiber dyed with the dyestuff as claimed in claim 5.

12. Fiber dyed with the dyestufi as' claimed in claim 6.

LEOPOLD LASKA. ARTHUR ZITSCHER. RUDOLF HEIL. 

